Production of ucu



United States Patent PRODUCTION OF UCM Myron B. Reynolds, Glenville, N. Y., and Harold L. Pickering, Tulsa, Okla., assignors to the United States of America as represented by the United States Atomic Energy Commission No Drawing. Application April 8, 1948, Serial No. 19,883

Claims. c1. 23-145) The present invention relates to activated uranium dioxide and refers particularly to the process of producing a highly active form of U02 which is characterized by rapid oxidation in air and rapid chlorination at elevated temperature.

Commercial U02 is ordinarily in the form of chocolate brown powder and does not possess the reactivity which characterizes the activated form of U02 produced by this process. In fact commercial U02 is stable in ordinary air at room temperature and exhibits no tendency to oxidize in ordinary air until it is heated to a temperature of the order of 100 C., under which conditions it is oxidized to the black oxide U308 in accordance with the following reaction:

Similarly, ordinary commercial forms of U02 may be chlorinated only at a moderate rate with C014 vapor to produce UC14; whereas the activated form of U02 produced by this invention may be rapidly chlorinated with CClq. vapor to produce U014.

Accordingly, it is an object of this invention to provide an activated form of U02.

Another object of the invention is to provide a highly active form of U02 which is characterized both by rapid oxidation in ordinary air at room temperature and rapid chlorination at an elevated temperature.

A further object of the invention is to provide a process for producing an activated form of U02 from U03.

A still further object of the invention is to provide a process for producing a highly activated form of U02 which is characterized by rapid oxidation in ordinaryair at room temperature and rapid chlorination with C014 vapor at an elevated temperature.

And a still further object of this invention is to provide a process for producing a highly active form of U02 which is particularly well suited for use as an intermediate in the production of UCl4.

Another further object of the invention is to provide a process of converting U03 to UCl4 by reducing U03 to the highly active U02 andthen subsequently chlorinating the activated U02 thus produced. 7

Still further objects of the present invention will be apparent from the following description taken in connection with the appended claims. 7

Broadly the objects of this invention are accomplished by treating U03 with an alcohol such as ethyl alcohol under optimum conditions and subsequently chlorinating the highly active form of U02 with C014 or S0Cl2 at elevated temperatures. The reduction of U03 to a highly active form of U02 with ethyl alcohol may be carried out under various conditions such as various temperatures, pressures, physical forms, and with various diluents and/or carriers. Although this reduction and activation may be accomplished over a range of temperature the optimum temperature for accomplishing the above stated objects has been ascertained to be between 200 C. and 425 C. and more particularly between 290 C. and

350 C. Also, although this process may be carried out without a diluent and/or carrier such as nitrogen gas, it has been ascertained that the reduction of U03 with ethyl alcohol can be carried out and controlled more readily and efficiently using nitrogen gas as the diluent and/or carrier.

The subsequent chlorination is usually performed at elevated temperatures between 250 C. and 500 C. with either C014 or S0Cl2. Carbon tetrachloride is usually employed as the chlorinating agent, as $0012 although a somewhat more reactive agent, in practice, is more difficult to handle than C014.

Prior to the chlorination and subsequent to the reduction the system may be purged by blowing a pure inert gas such as nitrogen over the activated U02.

More specifically in accordance with the present invention the active form of U02 is prepared by reducing U03 in a rotating'kiln-type reactor of stainless steel by the addition of ethanol either as a liquid from a dropping funnel connected through a metal tube to the reactor chamber or as a vapor by means of a. carrier gas, such as N2, which is bubbled through the ethanol heated to the proper temperature. Nitrogen is used as a diluent primarily to eliminate hazards of explosion should 02 be introduced into the system accidently and as a means to feed ethanol to the reaction and to assist in controlling the rate and temperature of the reaction. It is possible to obtain satisfactory control over the temperature of the exothermic reduction reaction by proper adjustment of furnace temperature, flow rate of N2 and the temperature of the bath employed to heat the alcohol. When the latter method, that of using N2 carrier, is employed, the rate of introduction of the ethanol may be controlled by the flow of N2 nd by the temperature to which the ethanol is heated. Since the reaction is exothermic, heat is evolved during the reaction and the internal temperature in the initial stages of the reaction is determined largely by the rate at which the ethanol is introduced. The temperature of the reacting mass is measured by means of a thermocouple contained in a thin-walled shielding tube placed in the vapor phase over the reacting charge. The external reactor temperature is measured by a couple placed between the reactor and furnace core and is controlled through a recording potentiometer. As the reaction tapers ed, the furnace temperature is brought up to a predetermined or optimum internal reaction temperature.

The optimum temperature for the most efiicient aad' U303 is formed first at as low a temperature as C and conversion to brown U02 takes place slowly at this temperature and more rapidly as the temperature is raised.

Utilizing this optimum temperature range for the best production of a highly active form of U02 through the reduction of U03 with ethanol 21 series of combined reduction and chlorination experiments were carried out giving the results listed in the table. These results show that activated U02 obtained by reducing U03 with ethanol by the process of this invention is an excellent intermediate for the conversion of U03 to UCLi. The reduction and chlorination operations were carried out in the same rotating kiln-type reactor of stainless steel. In general 1420 grams of U03. 150 to 200 cc. of ethanol Patented Jan. 31, 1956' and 800 cc. of CCL; were used in the combined reduction and subsequent chlorination operations. One convenient method of obtaining U03 comprises calcination of uranium peroxide. Experiment No. of the table showing a low reduction temperature is taken as a typical and illustrative example of the other experiments. In this experiment a 1420 gram charge of U03 heated to 150 C. in the rotating kiln-type reactor was reduced to'active U02 by the introduction of ethyl alcohol vapor in a nitrogen gas carrier to the reactor. The rate of introduction of nitrogen gas carrier, introduced through the ethyl alcohol chamber which was maintained at 69 to 74 C., and then into the reactor was varied between 5 and 7.5 cc. per second to raise and maintain the temperature of the reaction mass between 295 C. and 340 C. At the end of the eighty minutes after approximately 150 to 200 cc. of ethanol had been introduced into the reactor the reduction operation was substantially complete, and the system was purged by blowing pure nitrogen gas through the reactor. The activated U02 is then chlorinated by introducing C014 into the reactor in liquid form without a carrier at such a rate as to maintain the reaction temperature at approximately 400 C.; the furnace temperature being increased gradually to 400 C. as the reaction tapers oti. A chlorination temperature of approximately 400 C. appears to be most satisfactory. At lower temperatures the reaction proceeds too slowly; whereas at higher temperatures, the losses from the reaction chamber increase materially. As the chlorination reaction is also exothermic, the reaction temperature may be controlled by the rate at which CC14 is introduced and by the furnace temperature. At the end of ninety minutes after approximately 800 cc. of CCl4 had been introduced into the reactor the chlorination operation is substantially complete. Analysis of the results of this experiment show, as was noted also in the other experiments listed in Table I that the recovery of usable prod uct averaged around 99%, of which 99% was the uranium tetrachloride desired. The results of these combined reduction and chlorination operations are listed in the following table.

Table Product, Reduction Chlorination gggfi; Exp. tile Av. Max. Time, Av. Max. Time, U 0 0 Temp Temp Min. Temp. Temp Min. 2

380 410 90 395 405 125 1. 0. 40 360 385 62 440 455 90 1. 20 O. 03 360 390 80 400 415 95 1. S7 0. 15 355 385 80 395 410 95 1. 82 0. 355 390 90 405 420 95 1. 03 0. 19 350 370 85 395 410 95 0. 63 0. 39 345 360 65 395 405 95 1. 24 0. 340 365 65 395 410 150 0. 90 0. 42 335 365 385 400 90 O. 63 O. 49 325 350 65 395 405 90 0. 83 0. 44 305 335 445 463 37 0. 24 0. 42 300 335 410 455 90 0. 07 0. 68 300 345 395 415 100 0. 27 0. 93 300 335 80 400 420 0. 53 0. 84 295 340 70 400 415 95 0. 29 0. 83 290 335 95 395 410 0. 92 0. 42

An analysis of the table clearly shows that activated U02 prepared by reducing U03 with ethanol is a most excellent intermediate for producing UClr from uranium compounds such as U03 and that the optimum reduction temperature at which the most active form of U02 is obtained as tested by chlorination with C014 vapor is between 290 C. and 350 C.

The highly active form of U02 produced in accordance with the present process is far superior in activity to the commercial U02. This fact is readily evidenced by the special properties of the activated U02 as contrasted with the ordinary properties of commercial U02. For example, this activated U02 israpidly oxidized in ordinary air at room temperature, producing U308 whereas commercial U02 exhibits no oxidation in ordinary air until it is heated to a temperature of the order of 100 C. Also, this activated U02 may be rapidly and efiiciently chlorinated with CCLr vapor to produce U014; whereas commercial U02 may be chlorinated only at a moderate rate and much less efi'iciently.

Having broadly and specifically disclosed the present invention, it is apparent that many modifications and departures may be made without departing essentially from the nature and scope thereof as may be included within the following claims and it is intended to cover in the appended claims all such modifications as fall within the true spirit and scope of the disclosed invention.

We claim:

1. The process for producing a highly active form of U02 which is characterized by rapid oxidation in ordinary air at room temperature and rapid chlorination with carbon tetrachloride at approximately 400 C., comprising reducing U03 with a mixture of ethyl alcohol and an inert gaseous diluent at 200 to 425 C.

2. The process for producing a highly active form of U02 which is characterized by rapid oxidation in ordinary air at room temperature and rapid chlorination with carbon tetrachloride at approximately 400 C., comprising reducing U03 with a mixture of ethyl alcohol and nitrogen at a temperature within the range of 295 C. to 350 C.

3. The process of converting U03 to U014 which comprises reducing U03 with ethanol at 200 to 425 C., and chlorinating the activated U02 formed with carbon tetrachloride at 250 to 500 C.

4. The process of converting U03 to U014 which comprises reducing U03 with ethyl alcohol in a nitrogen diluent at temperatures ranging from 290 C. to 350 C. and chlorinating the highly active form of U02 produced with carbon tetrachloride at temperatures ranging from 390 C. to 420 C.

5. The process of converting U03 to U014 which comprises passing nitrogen gas through a bath of ethanol maintained at a temperature of 65 to 75 C. introducing the nitrogen diluted ethanol vapors thus produced into a reactor containing U03 heated to a temperature between C. and 300 C. at a rate sufiicient to raise and maintain the temperature at which U03 is being reduced between 290 C. and 350 C., blowing a current of pure nitrogen through the reactor after the reduction of U03 to U02 has been completed; and introducing CC14 into the reactor to chlorinate the highly active form of U02 at a rate sufficient to maintain a reaction temperature between 390 C. and 420 C.

References Cited in the file of this patent UNITED STATES PATENTS Logue et a1. Feb. 5, 1935 Oxley et a1. Dec. 15, 1936 OTHER REFERENCES 

1. THE PROCESS FOR PRODUCING A HIGHLY ACTIVE FORM OF UO2 WHICH IS CHARACTERIZED BY RAPID OXIDATION IN ORDINARY AIR AT ROOM TEMPERATURE AND RAPID CHLORINATION WITH CARBON TETRACHLORIDE AT APPROXIMATELY 400* C., COMPRISING REDUCING UO3 WITH A MIXTURE OF ETHYL ALCOHOL AND AN INERT GASEOUS DILUENT AT 200* TO 425* C. 